Ab initio and DFT study on 2H-isoxazol-5-one: Consequences of strong intermolecular hydrogen-bond formation in supramolecular structures

Ab initio and density-functional-theory (DFT) calculations on 2H-isoxazol-5-one (A), its linear dimer (LD), cyclic dimer (CD), and cyclic trimer (CT), have been performed with several basis sets in the gas phase, including electron correlation by second-order Møller-Plesset perturbation theory. The calculated complexation energy for the intermolecular H-bonded trimer as well as the corresponding geometric changes are in good agreement with the notion of resonance-assisted intermolecular H-bond formation. Bond distances and angles of the optimized geometry of CT are in accordance with the X-ray-diffraction data found on a trimeric supramolecular complex of parent compound 4-(2-methoxybenzyl)-3-phenyl-4H-isoxazol-5-one. Ab initio and DFT geometry optimizations are also reproducing exactly the large asymmetry in bond angles around the C=O group that is systematically present in all literature available X-ray data for analogous heterocyclic penta-atomic compounds